EP0027162A1 - UV-strahlungs- und/oder hitzehärtbare Überzugszusammensetzung - Google Patents
UV-strahlungs- und/oder hitzehärtbare Überzugszusammensetzung Download PDFInfo
- Publication number
- EP0027162A1 EP0027162A1 EP80104306A EP80104306A EP0027162A1 EP 0027162 A1 EP0027162 A1 EP 0027162A1 EP 80104306 A EP80104306 A EP 80104306A EP 80104306 A EP80104306 A EP 80104306A EP 0027162 A1 EP0027162 A1 EP 0027162A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating composition
- polymerizing
- bridge
- components
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Definitions
- the present invention relates to a coating composition which can be cured by an ultraviolet irradiating operation or the combination of the ultraviolet irradiating operation and a heating operation, and more particularly, to a composition with which a plastic molding or the other basic materials are coated and cured to form protective film, which is higher in surface hardness, and superior in scratch resistance and weather resistance.
- the plastic Since the plastic is generally lower in hardness, and inferior in abrasion resistance and scratch resistance, the molding is easy to be scratched in surface and is spoiled in transparency.
- the plastic components used in electric products containers and covers for electric cookers are scratched while they are used or while they are washed with a steel or nylon scrubbing-brush or the like, thus ruining their looks and sanitary condition.
- the transparent panels or covers for acoustic products are likely to be scratched during the use. Accordingly, the plastic components are restricted in use and is desired to be improved.
- coating compositions having such uses as described hereinabove, there are proposed many methods of coating organic silicone compound, melamine compound, etc. on the surfaces of base materials such as plastic molding, etc. thereby to form the cured film.
- coating compositions are not proposed in known methods, which can provide hardness of 7H or more in pencil hardness.
- the coating compositions are inferior in weather resistance and abrasion resistance, thus providing unsatisfactory results.
- the coating composition which can be improved in abrasion resistance is fragile in protective film and is easy to crack, while crack prevention results in inferior abrasion and scratch resistance.
- compositions proposed are of heat curing type, wherein a longer time is required to cure the compositions, and the coated compositions may be deformed and deteriorated due to heating operation, and the stable film of higher hardness cannot be obtained. Also, the pot life of each of the compositions is too short to withstand the use for a longer period of time.
- an object of the present invention is to provide a coating composition of such characters as described hereinabove which can eliminate the disadvantages inherent to the conventional one.
- a coating composition containing a bridge-polymerizing unsaturated compound having acryloile group or radical and/or methacryloile group or radical, and photo- polymerizing start agent and/or heat-polymerizing start agent.
- the coating composition of the present invention is applied on the surfaces of plastic construction to retain the characteristics of the plastic construction in terms of abrasion resistance, weather resistance, etc. Therefore, the present invention provides a quickly cured coating composition which can form a film superior in surface hardness, weather resistance, adherence, transparency or the like by performing a coating operation on the base material to cure it. The coating operation is performed directly on the base material by a coating method normally performed or is performed after proper prior treatment.
- the composition is cured through irradiation of the ultraviolet rays at the approximately normal temperature, is cured through heating to a heat resisting temperature or lower or is cured by. the combination of the ultraviolet irradiation and the heating.
- the film which is capable of the initial coating performance can be formed in an extremely short time.
- the coating composition of the present invention contains a bridge-polymerizing unsaturated compound having acryloile group or radical and/or methacryloile group or radical, and phot-polymerizing start agent and/or heat-polymerizing start agent.
- the coating composition contains solvent, viscosity modifier, etc. in accordance with the use, the coating method or the like.
- Epoxide acrylate series resin or epoxide methacrylate series resin is added without fail to the bridge-polymerizing unsaturated compound of the composition.
- the composition which is free from the epoxide (metha) acrylate series resin is good in surface hardness, it is inferior in adherence against the base material and contracts during the curing operation to cause cracks.
- these bridge-polymerizing unsaturated compound is a composition composed of different, plural components, which contains three components or more in functional group number (number of acryloile radicals or methacryloile radicals) per molecule in the proportion of 50% or more by weight and contains six components or more in total functional group number per molecule or six or more in total functional group number per molecule of the average molecular weight with considering the number of the functional groups.
- the functional group number per molecule or the functional group number per molecule of the average molecular weight is lower than six in total, the sufficient hardness of the film is not provided. Also, when three components or more in functional group number per molecule are not contained by 60% or more by weight, the composition is not provided, which forms superior film properly balanced in surface hardness, abrasion resistance,scratch resistance, weather resistance, adherence, etc.
- the bridge-polymerizing unsaturated compound containing the acryloile radical or the methacryloile radical has, within the molecule, ethylene unsaturated double bond shown by a general formula (wherein R in the formula represents hydrogen atoms or methyl group) in the chemical constitution.
- the bridge-polymerizing unsaturated compound can be provided with acrylic acid, methacrylic acid and mono or polyacrylic ester, methacrylic ester or the like such as acrylate or methacrylate of alkyl, cycloalkyl, glycyzirtetrahydro- furfuryl, allyl, hydroxyalkyl, alkylene glycol, poly- oxialkylene glycol, trimethyrollpropane, pentaerythritol or the like, and also, urethane (metha) acrylate resin, oligo-ester (metha) acrylate or the like are enumerated.
- epoxide (metha) crylate resin phenol novolak epoxide (metha) acrylate resin, cresol novolak epoxide (metha) acrylate resin, bisphenol A epoxide (metha) acrylate resin or the like are enumerated.
- a compound containing three or more in the functional group of acryloile radical or methacryloile radical shown by the above general formula there are numerated various photo-polymerizing oligomer such as trimethyroll propane triacrylate, dipentaerythritol, triacrylate or the like and oligo-ester acrylate, epoxide acrylate, urethane acrylate, melanine acrylate, silicone acrylate or the like.
- various polymerizing oligomer in addition to dipentaerythritol polyacrylate or the like, are enumerated.
- the polymerization start agent there are photo-polymerization start agent and heat-polymerization start agent.
- the photo-polymerization start agent there are enumerated mixtures of one type or two types or more of benzoin, benzoin alkyl ether, a substitution benzoin, anthraquinone, alkyl substitution anthraquinone, benzyl, benzophenone, triphenyl-phosphine dibenzir-ketone or the like.
- the heat-polymerization start agent there can be enumerated mixtures of one type or two types or more of organic peroxide such as benzoin peroxide, methyl ethyl keton peroxide, t-butyl hydro peroxide, cumene hydro peroxide, dicimil peroxide, t-butyl peroxide benzoate or the like or azo compound such as azobisisobutyro nitrile or the like.
- the heat polymerization start agent functions as cure promoting agent for the photo-polymerization start agent when the heat-polymerization start agent is used together with the photo-polymerization start agent.
- the viscosity can be lowered in accordance with the respective uses, as the orgahic solvent used for lower viscosity, mixed solvents of one or two or more of alcohols, ketones, ethers, esters or the like can be used.
- Ethyl alcohol, acetone, toluene, xylene or the like can be used for the proper use of the base material.
- acetone solvent or the like is not suitable for acrylic resin and AS resin, but mixed solvent such as ethyl alcohol, iso propyl alcohol, toluene or the like is particularly desired.
- the ultraviolet ray generating source used for curing the coating composition including the ordinary ultraviolet-ray-irradiation curing composition or the heat curing composition
- sunlight, low-pressure mercury-arc lamp, medium-pressure mercury-arc lamp, high-pressure mercury-arc lamp, superhigh-pressure mercury-arc lamp, arc lamp, xenon lamp or the like are enumerated.
- the heating source for the heat curing composition hot blast, nichrome heater wire, infrared ray lamp, far infrared ray heater or the like are enumerated.
- cobalt naphthenate, mangan naphthenate, amines, P-toluene sulfonamide, etc. are blended as cure promoting agent when required.
- bubble removing agent, viscosity increasing agent or the like can be added when required.
- the components of embodiments essentially comprise two functional (metha) acrylate components (c), three functional (metha) acrylate components (b), polyfunctional (six functional or more) epoxide (metha) acrylate components (a), and polymerization start agent component (d).
- Phenol novolak type epoxide acrylate (molecular weight 100 through 10000) as the components (a) trimethyroll propane triacrylate as the components (b), hydroxy ethyl methaacrylate as the components (c) and benzoin isopropyl ether as the component (d) were mixed respectively in given amounts, and repeatedly mixed and stirred for thirty minutes' melting operation in an oil bath at 80°C.
- the coating composition thus obtained was applied on the acrylic plate.
- the test results provided by a given test method as mentioned hereinbelow are given in the Table 1.
- the coated products listed within Tables 1 and 2 were measured in physical properties of adherence, pencil hardness, scratch resistance and weather resistance by the following methods.
- a pencil hardness measuring instrument was used for measuring the pencil hardness of the coated film with the load being 1000g.
- the face of the coated film was scrubbed with steel wool to show, in three stages, how the coated face was scratched.
- the coated films of embodiments which have been cured after the irradiation of the ultraviolet rays for a given period of time are hard to be scratched if the film are washed with a steel-scrubbing brush, a nylon brush or the like, thus keeping its original fine appearance.
- the coating film is provided which is superior in terms of-food sanitation.
- the compositions which are well balanced in characteristics as A in adherence, 7H or more in pencil hardness, A in scratch resistance, no change in weather resistance, etc., and are superior in characteristics, are provided in the embodiments 5 and 6.
- the compositions of embodiments 5 and 6 contain, respectively, three or more functional components in the proportion of 50% or more by weight, six or more components in the number of functional groups per molecule, and epoxide (metha) acrylate resin.
- the acrylate base plate and the AS base plates were used in tests, many various materials such as plastic materials, wood, etc. can be also applied.
- the heat-polymerization start agent can be jointly used to form the coating film, for an extremely short time, on complicated shapes.
- the coating compositions of the present invention can be reduced in viscosity, and only the coating operation by the dipping method can make film of several micrometers.
- the coating composition of the present invention contains a bridge-polymerizing unsaturated compound having acryloile group and/or methacryloile group, and photo-polymerizing start agent and/or heat-polymerizing start agent.
- the coating composition contains solvent, viscosity modifier, etc. in accordance with the use, the coating method or the like. Therefore, the present invention provides a quickly cured coating composition which can form.a film superior in surface hardness, weather resistance, adherence, transparency or the like by performing a coating operation on the base material to cure it.
- the coating operation of the composition is performed directly on the base material by a coating method normally performed or is performed after proper prior treatment, while the composition is cured through irradiation of the ultraviolet rays at the approximately normal temperature, is cured through heating to a heat resisting temperature or lower or is cured by the combination of the ultraviolet irradiation and the heating, and, also, the film which is capable of the initial coating performance can be formed in an extremely short time.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP98942/79 | 1979-08-01 | ||
JP9894279A JPS5622364A (en) | 1979-08-01 | 1979-08-01 | Coating composition |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0027162A1 true EP0027162A1 (de) | 1981-04-22 |
EP0027162B1 EP0027162B1 (de) | 1985-01-23 |
Family
ID=14233157
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80104306A Expired EP0027162B1 (de) | 1979-08-01 | 1980-07-23 | UV-strahlungs- und/oder hitzehärtbare Überzugszusammensetzung |
Country Status (5)
Country | Link |
---|---|
US (1) | US4404075A (de) |
EP (1) | EP0027162B1 (de) |
JP (1) | JPS5622364A (de) |
CA (1) | CA1182244A (de) |
DE (1) | DE3070009D1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997023524A1 (en) * | 1995-12-22 | 1997-07-03 | Alliedsignal Inc. | Thermosetting acrylic materials of high glass transition temperature |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57113434A (en) * | 1981-01-06 | 1982-07-14 | Mitsubishi Rayon Co Ltd | Manufacture of information recording body |
JPS5943015A (ja) * | 1982-09-02 | 1984-03-09 | Toyobo Co Ltd | 硬化型樹脂組成物 |
GB2131026B (en) * | 1982-09-22 | 1986-04-09 | Daicel Chem | Modified epoxy (meth) acrylate resin and hardenable resin composition containing the same |
NL8300685A (nl) * | 1983-02-24 | 1984-09-17 | Philips Nv | Optisch uitleesbare informatiedrager voorzien van een mantel uit verknoopte kunststof. |
US4722947A (en) * | 1985-08-05 | 1988-02-02 | Pony Industries, Inc. | Production of radiation curable partial esters of anhydride-containing copolymers |
US4745138A (en) * | 1985-08-05 | 1988-05-17 | Pony Industries, Inc. | Radiation curable partial esters of anhydride-containing copolymers |
JPH01141908A (ja) * | 1987-11-30 | 1989-06-02 | Dainippon Ink & Chem Inc | 活性エネルギー線硬化性樹脂組成物 |
WO1992000588A1 (en) * | 1990-07-02 | 1992-01-09 | Teijin Limited | Optical disk |
US6559222B1 (en) | 1997-10-16 | 2003-05-06 | Sun Chemical Corporation | Photoneutralization of pH sensitive aqueous polymeric dispersions and methods for using same |
US6156816A (en) * | 1998-08-20 | 2000-12-05 | Henkel Corporation | Screen coating composition and method for applying same |
US6225389B1 (en) | 1998-08-20 | 2001-05-01 | Henkel Corp. | Screen coating composition and method for applying same |
US6211308B1 (en) | 1998-08-20 | 2001-04-03 | Henkel Corporation | Method for coating a textile |
JP3903715B2 (ja) * | 2000-12-26 | 2007-04-11 | 大日本インキ化学工業株式会社 | エネルギー線硬化型樹脂組成物および塗膜形成方法 |
US20070222093A1 (en) * | 2004-04-22 | 2007-09-27 | Takeshi Furuta | Production Method for Graded Index Type Optical Transmission Element |
US20080003373A1 (en) * | 2005-05-11 | 2008-01-03 | Yazaki Corporation | Antireflective coating compositions and methods for depositing such coatings |
JP5557274B2 (ja) * | 2009-10-20 | 2014-07-23 | 日本化薬株式会社 | 紫外線硬化型ハードコート樹脂組成物、それを用いたハードコートフィルム及びハードコート成形物 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2534012A1 (de) * | 1975-07-30 | 1977-02-17 | Bayer Ag | Haertbare ueberzugsmittel |
GB1476528A (en) * | 1973-10-04 | 1977-06-16 | Bayer Ag | Highly reactive resin compositions hardenable by uv-light |
DE2631949A1 (de) * | 1976-07-15 | 1978-01-19 | Bayer Ag | Strahlen-haertende bindemittel |
DE2807605A1 (de) * | 1977-02-23 | 1978-09-14 | Mitsubishi Rayon Co | Beschichtungsmasse und verfahren zur herstellung eines abriebfesten kunstharzformkoerpers |
GB1544025A (en) * | 1976-11-01 | 1979-04-11 | Eastman Kodak Co | Radiation-curable coating compositions |
DE2847796A1 (de) * | 1977-11-03 | 1979-05-17 | Somar Mfg | Strahlungshaertbare harzmasse |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1576470A1 (de) | 1967-06-22 | 1970-02-05 | Bosch Gmbh Robert | Kraftstoffeinspritzpumpe |
US3674545A (en) * | 1970-04-07 | 1972-07-04 | Du Pont | Radiation curable epoxy coating composition and method of coating |
US3673140A (en) * | 1971-01-06 | 1972-06-27 | Inmont Corp | Actinic radiation curing compositions and method of coating and printing using same |
US3715293A (en) * | 1971-12-17 | 1973-02-06 | Union Carbide Corp | Acetophenone-type photosensitizers for radiation curable coatings |
FR2255629B1 (de) | 1973-12-20 | 1976-10-22 | Ibm | |
US4040925A (en) * | 1974-05-02 | 1977-08-09 | Scm Corporation | Ultraviolet curing of electrocoating compositions |
US4017652A (en) * | 1974-10-23 | 1977-04-12 | Ppg Industries, Inc. | Photocatalyst system and ultraviolet light curable coating compositions containing the same |
US3992477A (en) * | 1974-12-31 | 1976-11-16 | Ford Motor Company | Protective coating composition |
US4237216A (en) * | 1978-12-08 | 1980-12-02 | International Business Machines Corporation | Photosensitive patternable coating composition containing novolak type materials |
-
1979
- 1979-08-01 JP JP9894279A patent/JPS5622364A/ja active Granted
-
1980
- 1980-07-23 EP EP80104306A patent/EP0027162B1/de not_active Expired
- 1980-07-23 DE DE8080104306T patent/DE3070009D1/de not_active Expired
- 1980-07-31 CA CA000357409A patent/CA1182244A/en not_active Expired
-
1982
- 1982-11-30 US US06/445,472 patent/US4404075A/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1476528A (en) * | 1973-10-04 | 1977-06-16 | Bayer Ag | Highly reactive resin compositions hardenable by uv-light |
DE2534012A1 (de) * | 1975-07-30 | 1977-02-17 | Bayer Ag | Haertbare ueberzugsmittel |
DE2631949A1 (de) * | 1976-07-15 | 1978-01-19 | Bayer Ag | Strahlen-haertende bindemittel |
GB1544025A (en) * | 1976-11-01 | 1979-04-11 | Eastman Kodak Co | Radiation-curable coating compositions |
DE2807605A1 (de) * | 1977-02-23 | 1978-09-14 | Mitsubishi Rayon Co | Beschichtungsmasse und verfahren zur herstellung eines abriebfesten kunstharzformkoerpers |
DE2847796A1 (de) * | 1977-11-03 | 1979-05-17 | Somar Mfg | Strahlungshaertbare harzmasse |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997023524A1 (en) * | 1995-12-22 | 1997-07-03 | Alliedsignal Inc. | Thermosetting acrylic materials of high glass transition temperature |
Also Published As
Publication number | Publication date |
---|---|
US4404075A (en) | 1983-09-13 |
EP0027162B1 (de) | 1985-01-23 |
CA1182244A (en) | 1985-02-05 |
DE3070009D1 (en) | 1985-03-07 |
JPS5622364A (en) | 1981-03-02 |
JPH0140063B2 (de) | 1989-08-24 |
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